Composite metal foam and method of preparation thereof

ABSTRACT

The present invention is directed to composite metal foams comprising hollow metallic spheres and a solid metal matrix. The composite metal foams show high strength, particularly in comparison to previous metal foams, while maintaining a favorable strength to density ratio. The composite metal foams can be prepared by various techniques, such as powder metallurgy and casting.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a Continuation-In-Part of U.S. patentapplication Ser. No. 12/639,581, filed Dec. 16, 2009, which is aDivisional of U.S. patent application Ser. No. 11/289,661, filed Nov.29, 2005, now U.S. Pat. No. 7,641,984, which claims priority to U.S.Prov. Pat. App. No. 60/631,801, filed Nov. 29, 2004, the disclosures ofwhich are incorporated herein by reference in their entireties.

FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

The research underlying this invention was supported in part with fundsfrom National Science Foundation (NSF) Grant No. 0238929. The UnitedStates Government may have an interest in the subject matter of thisinvention.

FIELD OF THE INVENTION

The present invention is directed to composite metal foams and methodsof preparation thereof. The composite metal foams generally comprisehollow metallic spheres and a solid metal matrix.

BACKGROUND

Metallic foams are a class of materials with very low densities andnovel mechanical, thermal, electrical, and acoustic properties. Incomparison to conventional solids and polymer foams, metal foams arelight weight, recyclable, and non-toxic. Particularly, metal foams offerhigh specific stiffness, high strength, enhanced energy absorption,sound and vibration dampening, and tolerance to high temperatures.Furthermore, by altering the size and shape of the cells in metal foams,mechanical properties of the foam can be engineered to meet the demandsof a wide range of applications.

Various methods are presently known in the art for preparing metallicfoams. According to one method, metal powders are compacted togetherwith suitable blowing agents, and the compressed bodies are heated abovethe solidus temperature of the metal matrix and the decompositiontemperature of the blowing agent to generate gas evolution within themetal. Such “self-expanding foams” can also be prepared by stirring theblowing agents directly into metal melts. Metallic foams can also beprepared as “blown foams” by dissolving or injecting blowing gases intometal melts. Metallic foams can also be prepared by methods whereingasses or gas-forming chemicals are not used. For example, metal meltscan be caused to infiltrate porous bodies which are later removed aftersolidification of the melt, leaving pores within the solidifiedmaterial.

Metallic foams have been shown to experience fatigue degradation inresponse to both tension and compression. Plastic deformation undercyclic loading occurs preferentially within deformation bands, until thedensification strain has been reached. The bands generally form at largecells in the ensemble, mainly because known processes for producingthese materials do not facilitate formation in a uniform manner. Suchlarge cells develop plastically buckled membranes that experience largestrains upon further cycling and will lead to cracking and rapid cyclicstraining. As a result, the performance of existing foams has not beenpromising due to strong variations in their cell structure (see Y.Sugimura, J. Meyer, M. Y. He, H. Bart-Smith, J. Grenstedt, & A. G.Evans, “On the Mechanical Performance of Closed Cell Al Alloy Foams”,Acta Materialia, 45(12), pp. 5245-5259).

In the production of closed cell metallic foams, one obstacle is theinability to finely control cell size, shape, and distribution. Thismakes it difficult to create a consistently reproducible material wherethe properties are known with predictable failure. One method forcreating a uniform closed cell metallic foam is to use prefabricatedspheres of a known size distribution and join them together into a solidform, such as through sintering of the spheres, thereby forming a closedcell hollow sphere foam (HSF).

Hollow metal spheres, such as those available from Fraunhofer Institutefor Manufacturing and Advanced Materials (Dresden, Germany), can beprepared by coating expanded plastic spheres (e.g., polystyrene) with apowdered metal suspension. The spheres are then placed into a mold andare heated to pyrolize the polystyrene and powder binder, and to sinterthe metal powder into a dense, solid shell. Metal foams previouslyprepared through sintering of such hollow metal spheres are plagued bylow strength. Foams prepared by sintering metal spheres made ofstainless steel, when under compression, have been shown to undergodensification at a stress of approximately 2 to 7 MPa, reaching a strainof over 60%.

Accordingly, it is desirable to have metallic foams wherein cell size,shape, and distribution are controllable, and wherein high strength isexhibited. Such goals are achieved by the composite metal foams of thepresent invention and the methods of preparation thereof.

SUMMARY OF THE INVENTION

The present invention is a composite metallic foam comprising hollowmetal spheres and a solid metal matrix. The foam exhibits low densityand high strength. Generally, the composite metallic foam is prepared byfilling in the spaces around the hollow metallic spheres, thus creatinga solid matrix. Such preparation can be by various methods, includingpowder metallurgy techniques and casting techniques. The compositemetallic foams of the invention have unique properties that provide usein multiple applications, such as marine structures, space vehicles,automobiles, and buildings. The foams are particularly useful inapplications where weight is critical and vibration damping, as well asenergy absorption, are useful, such as blast panels for militaryapplications and crumple zones for automotive crash protection. Theapplication of the foams can also be extended into biomedicalengineering as medical implants and even to civil engineering forearthquake protection in heavy structures.

The composite metal foams of the invention, partly due to theircontrolled porosity (through use of preformed hollow metallic pieces)and foam cell wall support (through addition of a metal matrixsurrounding the hollow metallic pieces), exhibit highly improvedmechanical properties, particularly under compression loading.Accordingly, the strength of the inventive composite metal foams is manytimes higher than other metallic hollow sphere foams. Furthermore, theenergy absorption of the inventive foams is much greater than the bulkmaterial used in the foams (on the order of 30 times to 70 timesgreater), while the inventive foams also maintain a density well belowthat of the bulk materials.

In one aspect of the invention, there is provided a composite metal foamcomprising a plurality of hollow pieces (preferably hollow metallicpieces) and a metal matrix generally surrounding the hollow pieces. Thehollow pieces and the matrix can be comprised of the same or differentmaterials. In one embodiment, the hollow pieces are metallic spherescomprising steel, and the metal matrix comprises steel. In anotherembodiment, the metal matrix comprises aluminum, while the hollowspheres comprise steel.

According to another aspect of the invention, there is provided a methodof preparing a composite metallic foam comprising placing a plurality ofhollow metallic pieces in a mold and filling the spaces around thehollow metallic pieces with a metal matrix-forming material. The methodcan be carried out through the use of various techniques, such as powdermetallurgy or metal casting.

In one particular embodiment according to this aspect of the invention,the method comprises the following steps: arranging a plurality ofhollow metallic pieces in a mold; filling the spaces around the hollowmetallic pieces with a matrix-forming metal powder; and heating the moldto a sintering temperature, thereby forming a solid metal matrix aroundthe hollow metallic pieces. Various packing techniques, such asvibrating the mold according to a specific frequency, or varyingfrequencies, can be used for maximizing packing density of the metallicpieces within the mold. Further, such techniques can also be used duringthe step of filling the spaces around the hollow metallic pieces tofacilitate movement of the metal powder through the mold and around thehollow metallic pieces.

The method can further comprise applying pressure to the hollow metallicpieces and the matrix-forming metal powder within the mold, as wouldcommonly be done in powder metallurgy techniques. Such compressionwithin the mold can be carried out for the duration of the sinteringstep of the method.

According to another embodiment of the invention, the method comprisesthe following steps: arranging a plurality of hollow metallic pieces ina mold; casting a matrix-forming molten metal into the mold, therebyfilling the spaces around the hollow metallic pieces; and solidifyingthe liquid metal, thereby forming a metal matrix around the hollowmetallic pieces. As noted above, various packing techniques, such asvibrating the mold, can be used for maximizing packing density of themetallic pieces within the mold.

In a further aspect, the present invention can provide compositematerials formed of multiple layers. The multiple layers can eachprovide different functions and can provide the composite overall with aset of desirable characteristics. The inclusion of a composite metalfoam according to the present invention can provide the compositematerials with excellent properties in relation to overall low weight,excellent impact resistance and energy absorption, and favorablecharacteristics that can mimic surrounding materials, particularlynatural tissues.

In certain embodiments, the invention thus provides an energy absorptionpanel. Such panels, based on the combination of materials, can providefor absorption of a variety of types of energy including, but notlimited to, thermal energy, radiation, and kinetic energy. In someembodiments, such an energy adsorption panel can comprise a plurality oflayers of different material, at least one layer including a compositemetal foam comprising a plurality of hollow metallic spheres arrangedwith an interstitial space between the spheres, the interstitial spacebeing filled with a solid metal matrix. In particular, the hollowmetallic spheres have an average diameter of about 0.5 mm to about 20mm. Further, the hollow metallic spheres have an average wall thicknessthat is about 1% to about 15% of the average sphere diameter and canhave an average wall porosity of less than about 12%. The compositemetal foam layer can impart very desirable characteristics to the panel.For example, the composite metal foam layer can have a strength,evaluated as the plateau stress, of at least 35 MPa, can have a densityof less than about 4 g/cm³, can exhibit an energy absorption of at leastabout 20 MJ/m³, and can exhibit a modulus of elasticity of less than 50GPa. The hollow metallic spheres and the solid metal matrix can beformed of the same metal or metal alloy. Alternatively, the hollowmetallic spheres and the solid metal matrix can be formed of differentmetals or metal alloys. For example, the hollow metallic spheres cancomprise a metal or metal alloy selected from the group consisting ofiron, iron alloy, steel, aluminum, aluminum alloy, chromium, titanium,cobalt lead, nickel, manganese, molybdenum, copper, and combinationsthereof. Likewise, the solid metal matrix can comprise a metal or metalalloy selected from the group consisting of iron, iron alloy, steel,aluminum, aluminum alloy, chromium, titanium, cobalt lead, nickel,manganese, molybdenum, copper, and combinations thereof. The solid metalmatrix specifically can be formed of a sintered mass of metal particles.For example, the solid metal matrix can be a sintered mass of a mixtureof metal powders formed of a first metal powder having a first averageparticle size and at least a second metal powder having a second,different average particle size. Particle sizes can be in the range ofabout 1 μm to about 200 μm.

In addition to the composite metal foam, the energy absorption panels ofthe invention can comprise further, different layers. For example, thepanel can comprise a ceramic layer and/or a cloth layer. An exemplarycloth layer can be formed of fibers of a natural material and/or asynthetic material, such as an aramid fiber.

Ceramic layers and/or cloth layers can be particularly useful in theformation of personal protection articles. Thus, the invention furthercan provide a personal protection article comprising an energyabsorption panel as described herein. Exemplary personal protectionarticles can include headgear, body armor, and footwear. In particularembodiments, an article according to the invention can be formed of anenergy absorption panel comprising a layer including the composite metalfoam sandwiched between a ceramic layer and a cloth layer or polymerlayer. A personal protection article can be particularly characterizedin relation to its specific energy absorption properties. For example,an article according to the invention can exhibit sufficient energyabsorption such that the energy of a projectile (e.g., of a mass ofabout 10 g or less) traveling at a velocity of about 200 m/s iscompletely absorbed by the article without full penetration of theprojectile through the article. In another example, the article can beeffective to absorb an impact energy of about 2,000 Joules or greater.

In addition to absorbing kinetic energy, an energy absorption panelaccording to the invention also can be effective for absorbing orshielding against radiation energy. In such embodiments, a panelaccording to the invention can comprise a layer including an open cellfoam (e.g., a metal foam, such as aluminum, or a polymer foam, such aultra high strength polyethylene). In some embodiments, the open-cellfoam can be at least partially filled with secondary media. For example,the secondary medium can fill about 5% to 100%, about 10% to about 99%,about 15% to about 98%, or about 20% to about 95% by volume of the porevolume in the open-cell foam. The secondary media can comprise a varietyof materials, such as water, waxes, polymers, and combinations thereof.The panel further can comprise a radiation shielding material, which canbe a component provided separate from the other components or can becombined with any of the further components of the panel. For example,such shielding material can comprise a liquid material, particularly anaqueous material, such as water or borated water. Preferably, theradiation shielding material comprises a material effective againstradiation selected from the group consisting of neutron radiation,cosmic radiation, x-ray radiation, gamma radiation, and combinationsthereof. Still further, an energy absorption panel can comprise one ormore layers of a non-foam material, which can be selected from the groupconsisting of metals, natural polymers, synthetic polymers, andcombinations thereof. The non-foam layer can include a radiationshielding material, such as a boron coating, or can comprise boratedpolyethylene. In a specific embodiment, an energy absorption panel cancomprise a composite metal foam layer separated from an open cell foamlayer by a non-foam layer. Such sandwich panel can further includeadditional non-foam layers on the external surface of the compositemetal foam layer and/or on the external surface of the open-cell foamlayer.

In addition to the foregoing, the present invention also can becharacterized in relation to a variety of structures that can be formedfrom the composite metal foam. Thus, in certain embodiments, theinvention can provide a structure including a composite metal foamcomprising a plurality of hollow metallic spheres, such as with anaverage diameter of about 0.5 mm to about 20 mm, an average wallporosity of less than about 12%, and an average wall thickness of about1% to about 15% of the average sphere diameter. The spheres can bearranged with an interstitial space between the spheres, theinterstitial space being filled with a solid metal matrix. Preferably,the composite metal foam can exhibit a strength, evaluated as theplateau stress, of at least 35 MPa, a density of less than about 4g/cm³, and an energy absorption of at least about 20 MJ/m³. Thecomposite metal foam generally can be formed of the various materials asalready noted above and as further described herein.

In some embodiments, a structure according to the invention can be acomponent of an aerospace vehicle. For example, the structure can be ajet engine component (e.g., a jet engine fan blade). Further, thestructure can be an airplane or space vehicle body component. As alreadynoted above, the composite metal foam structure can be combined anopen-cell foam that, optionally, can include a radiation shieldingmaterial as otherwise described herein. In further embodiments, thestructure can be a landing component of an aerospace vehicle (e.g., alanding gear on an airplane or a landing skid on a helicopter).

In additional embodiments, a structure according to the invention can bea component of a building. Specifically, the structure can be a shockabsorbing brace. Other building components also are encompassed, asotherwise discussed herein.

Still further, a structure according to the invention can be a componentof an automobile. In particular, the automobile component can be a shockabsorbing component. Any structural element of an automobile (or othermoving vehicle) that can be formed of a metal can be made using thecomposite metal foam of the invention.

In a particularly beneficial embodiment, a structure according to theinvention can be a component of medical device. For example, thestructure can be a bone implant, which is particularly useful in thatthe implant can be functionally graded in porosity. The porosity can beless at the outer edge of the implant than in the middle of the implant.Thus, the average diameter of the hollow metallic spheres can increasefrom the outer edge of the implant to the middle of the implant. Theimplant can significantly mimic natural bone—e.g., the implant can havea modulus of elasticity of less than 50 GPa (i.e., substantially closeto the average modulus of elasticity of natural bone—about 17 GPa). Thebone implant can have a modulus of elasticity that is within 80% of theaverage modulus of elasticity of natural bone. In further embodiments,the bone implant can have a modulus of elasticity that is within about50% of the modulus of elasticity of the natural bone of a subjectreceiving the implant. The medical device can be selected from a varietyof materials. For example, the bone implant can be a dental implant oran orthopedic implant. In other embodiments, the medical device can be amedical or dental tool.

In other embodiments, other materials already described above can becharacterized in relation to structures provided according to theinvention. For example, the inventive structure can be a personalprotection article, such as headgear, body armor, or footwear. Likewise,the structure can be a blast panel.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an optical image providing a cross-sectional view of a 3.7 mmhollow metallic sphere useful according to the present invention;

FIG. 2 is a cross-sectional view of a composite metal foam of theinvention comprising hollow steel spheres surrounded by a metal matrixformed by powder metallurgy using steel powder;

FIG. 3 is a detailed cross-sectional view of a composite metal foamformed by powder metallurgy, according to one embodiment of theinvention, comprising hollow steel spheres surrounded by a steel matrix;

FIG. 4 is a cross-sectional view of the composite metal foam shown inFIG. 3 providing an even greater detailed view of the metal matrix;

FIG. 5 is a SEM image of the composite metal foam of FIG. 2 showing across-section of two steel spheres in contact with each other and thesteel matrix filling the interstitial spaces;

FIG. 6 is another SEM image of the composite metal foam of FIG. 2showing a cross-section of two spheres not in contact and the steelmatrix filling the spaces between and around the spheres;

FIG. 7 is a three-dimensional drawing of a permanent casting mold usefulin one embodiment of the invention;

FIG. 8 is a cross-sectional view of a permanent casting mold useful inone embodiment of the invention;

FIG. 9 is a cross-sectional view of a composite metal foam of theinvention formed by casting molten aluminum around hollow steel spheres;

FIG. 10 is a SEM image of a cross-section of a composite metal foam ofthe invention showing an aluminum matrix between two hollow steelspheres;

FIG. 11 is a detailed view of the SEM image from FIG. 10 showing theinterface between the aluminum matrix and the steel wall of the hollowsphere;

FIG. 12 is a SEM image of a cross-section of a composite metal foam ofthe invention formed by casting an aluminum matrix around hollow steelspheres and shows (a) four spheres embedded in the matrix with a visiblevoid at the interface of two spheres, and (b) a detail view of thealuminum matrix showing the different phases present;

FIG. 13 is a cross-sectional optical image of three composite metalfoams prepared according to various embodiments of the invention;

FIG. 14 is a chart of the stress-strain curves of composite metal foamsaccording to various embodiments of the invention under monotoniccompression;

FIG. 15 shows a stainless steel composite metal foam according to oneembodiment of the invention both before and after compression testingwith 60% strain;

FIG. 16 is a chart showing a curve of strain versus number of cyclesduring a compression fatigue test of a cast composite metal foamaccording to one embodiment of the invention; and

FIG. 17 shows optical images of a cast composite metal, according to oneembodiment of the invention, before and during a compression fatiguetest.

DETAILED DESCRIPTION OF THE INVENTION

The invention now will be described more fully hereinafter withreference to the accompanying drawings, in which preferred embodimentsof the invention are shown.

These embodiments are provided so that this disclosure will be thoroughand complete, and will fully convey the scope of the invention to thoseskilled in the art. Indeed, the invention may be embodied in manydifferent forms and should not be construed as limited to theembodiments set forth herein; rather, these embodiments are provided sothat this disclosure will satisfy applicable legal requirements. As usedin the specification, and in the appended claims, the singular forms“a”, “an”, “the”, include plural referents unless the context clearlydictates otherwise.

The composite metallic foam of the present invention combines theadvantages of metal matrix composites with the advantages of metallicfoams to provide higher strength metallic foams of controlled porosity.The composite metal foams generally comprise a plurality of hollowmetallic pieces and a metal matrix filling the spaces around themetallic pieces.

Metal matrix composites are generally understood to be metals that arereinforced with various materials. Such materials can include natural orsynthetic fibers or particulate matter. Materials particularly usefulinclude boron, silicon carbide, graphite, alumina tungsten, beryllium,titanium, and molybdenum. Fibers may be continuous filaments ordiscontinuous fibers. Examples of natural discontinuous fibers includehair or whiskers. The reinforcements, of which the above are onlynon-limiting examples thereof, can be chosen for specific purposes, suchas increasing stiffness, strength, heat resistance, and wear resistance.Combining the advantages of metal matrix composites with the advantagesof metal foams results in the composite metal foams of the invention,which exhibit increased strength, as well as additional beneficialproperties as discussed herein.

The composite metal foams of the invention comprise hollow pieces. In aparticular embodiment of the invention, the hollow pieces are sphericalin shape (i.e., “hollow spheres”). While such a shape is particularlyuseful, the hollow pieces comprising the composite metal foam can alsotake on other geometric shapes as could be beneficial for impartingimproved properties to the finished composite metal foam. Forsimplicity, the hollow pieces used in the invention are described hereinby the particular spherical embodiment. However, description of thehollow pieces as spheres is not intended to limit the scope of thehollow pieces, which can take on other shapes.

The hollow spheres used in the composite metal foams of the inventioncan comprise any material that would be useful for providing strength inan overall composite foam of the invention and can withstand thepreparation process, such as powder metallurgy or casting, as describedherein. In one preferred embodiment, the hollow spheres are metallic.

Hollow metallic spheres, according to the invention, can comprise anymetal generally recognized as being useful for preparing metal foams,metal matrix composites, or other metal components useful in variousindustries, such as automotive, aerospace, construction, safetymaterials, and the like. Particularly useful are metals commonly used inapplications where lightweight materials, or materials exhibitingrelatively low density, are desirable. For example, the hollow spherescan comprise iron (and alloys thereof), aluminum, titanium, nickel,ceramics, such as alumina and silica carbide, and the like. The metalscomprising the hollow spheres can be a single, essentially pure metal;however, the term metal, as used herein to describe the components ofthe composite metal foams of the invention, can also refer to metalmixtures, including alloys, intermetallic compounds, such as titaniumaluminide, and the like. Further, the metals can include tracecomponents as would be recognizable as being beneficial, as well asnon-detrimental trace impurities. In one particularly preferredembodiment, the hollow metallic spheres are comprised of steel, such asstainless steel or low carbon steel. The composition of one type of lowcarbon steel and one type of stainless steel (316L stainless steel)useful in particular embodiments of the invention are provided in Table1.

TABLE 1 Exemplary Metal Compositions for Hollow Metallic Spheres TypeComposition Low Carbon <0.007% carbon and 0.002% oxygen; remainingbalance Steel: iron 316L Stainless 0.03% carbon, 0.3% oxygen, 17%chromium, 13% Steel: nickel, 0.9% silicon, 0.2% manganese, 2.2% molybde-num, and remaining balance iron

The average size of the hollow metallic spheres can vary depending uponthe desired physical properties of the finished composite metal foam.Average size of the spheres is generally evaluated in terms of spherediameter. When considering the physical properties of the finishedcomposite metal foam, though, sphere wall thickness must also beconsidered. Accordingly, assuming sphere wall thickness remainsunchanged, the use of spheres having a greater average diameter would beexpected to result in a finished composite metal foam of lower densitythan if spheres of smaller average diameter are used. The averagediameter is also limited by the size and dimensions of the finishedcomposite metal foam. For example, if the desired finished compositemetal foam is a metal sheet having a 25 mm thickness, the hollowmetallic spheres would necessarily need to have an average diameter ofless than 25 mm.

The hollow metallic spheres used in the invention generally have anaverage diameter of about 0.5 mm to about 20 mm. Preferably, the sphereshave an average diameter of about 1 mm to about 15 mm, more preferablyabout 1.5 mm to about 10 mm, still more preferably about 2 mm to about 8mm, most preferably about 2.5 mm to about 6 mm. In one particularembodiment, hollow metallic spheres having an average diameter of about3 mm to about 4 mm (nominally about 3.7 mm) have been used to preparethe composite metal foam of the invention. Depending upon the desiredproperties of the composite metal foam, other sphere sizes can also beused.

As noted above, sphere size is also described by the sphere wallthickness, which similarly affects the physical properties of thefinished composite metal foams. For example, assuming sphere averagediameter is unchanged, the use of spheres having a lesser average wallthickness would be expected to result in a finished composite metal foamof lower density than if spheres of greater average wall thickness areused. Accordingly, in one embodiment of the invention, it is desirableto minimize wall thickness. If wall thickness is too minimal, though,strength of the finished composite metal foams can be compromised. It istherefore beneficial to use spheres wherein the ratio of wall thicknessto average sphere diameter is in a range where density of the finishedcomposite metal foam is minimized but overall strength of the compositemetal foam is not appreciably sacrificed.

The hollow metallic spheres of the invention generally have an averagewall thickness that is about 1% to about 30% of the average diameter ofthe spheres. Preferably, the average sphere wall thickness is about 1%to about 15% of the average sphere diameter, more preferably about 1.5%to about 10%, still more preferably about 2% to about 8%, and mostpreferably about 2.5% to about 7% of the average sphere diameter. In oneparticular embodiment, the average sphere wall thickness is about 5% ofthe average sphere diameter. A cross-section of a hollow metallicsphere, such as useful according to the invention is shown in FIG. 1(note that the sphere in the figure has not been cut through thediameter of the sphere). As seen in the Figure, the sphere walls have agenerally uniform thickness. This is particularly advantageous in thatcomposite metal foams, according to the invention, can be prepared touniform porosity, said porosity being easily adjustable by use of hollowmetallic spheres of a desired average diameter and average wallthickness.

Preferentially, the percentage and size of porosities in the spherewalls are minimized to increase stability of the spheres duringprocessing of the foams. For example, when casting techniques are usedin preparing the composite metal foams, minimizing sphere wall porositydecreases the possibility of the matrix-forming molten metal penetratingthe cavities of the spheres. Such penetration should be avoided asfilling of the cavities could reduce the overall pore volume of thecomposite metal foam, unnecessarily increasing the overall density ofthe foam. In one embodiment, sphere wall porosity is less than about12%. Preferably, sphere wall porosity is less than about 10%, morepreferably less than about 8%, most preferably about 5% or less.

In addition to the hollow metallic pieces, the composite metal foam ofthe invention also comprises a matrix surrounding the hollow metallicpieces. The matrix generally comprises a metal, and the type of metalcomprising the matrix can be varied depending upon the technique used inpreparing the composite metal foam of the invention.

According to one embodiment, the metal comprising the matrix can be thesame metal type comprising the hollow metallic pieces. According toanother embodiment, the metal comprising the matrix is a different metaltype than that comprising the hollow metallic pieces. Preferably, themetal matrix includes a metal that is generally lightweight but stillexhibits good strength attributes. The use of such metals is beneficialfor maintaining a high strength to density ratio in the finishedcomposite metal foam of the invention. As before, the metal comprisingthe metal matrix can be an essentially pure single metal or can be amixture of metals. In one particular embodiment, the metal matrixcomprises steel. In another embodiment, the metal matrix comprisesaluminum.

Matrix composition may at least partially be dependant upon the methodof preparation of the composite metal foam. The composite metal foams ofthe invention can be prepared through various techniques known in theart. While the use of such techniques would not be readily apparent forpreparing composite metal foams, one of skill in the art, with thebenefit of the present disclosure, could envision similar techniqueswhich could be used in preparing the composite metal foams of theinvention. Such further techniques are also encompassed by the presentinvention.

According to one embodiment of the invention, there is provided a methodfor preparing a composite metal foam by powder metallurgy. According tothis method, the hollow metallic spheres are first placed inside a mold.At this point, it should be noted that the composite metal foam can beprepared directly in the final desired shape through use of a molddesigned to provide the desired shape. Alternately, the composite metalfoam may be prepared as a “stock” piece (e.g., a large rectangle) andthen be cut to the desired final shape. The size of the composite metalfoam prepared according to this embodiment of the invention is generallylimited by the size of the mold.

The metallic spheres are preferentially arranged in the mold to be in aspecific packing arrangement. Desirably, the packing arrangement is suchthat the metallic spheres are in their most efficient packing density(i.e., most closely packed). As such, the open space between the spheresis minimized, and the number of spheres arranged in the mold ismaximized. In this packing arrangement, the porosity of the finishedcomposite metal foam is maximized, which correlates into a minimizeddensity.

The arrangement of the metallic pieces in the mold can be facilitatedthrough mechanical means, such as vibrating the mold. In embodimentswhere metallic spheres are used, vibration is particularly useful as thespheres tend to “settle” into a most preferred packing density. Forexample, such vibration can be performed using an APS Dynamics model 113shaker and an APS model 114 amplifier with a General Radio 1310-Bfrequency generator. Vibrating at specific frequencies may be beneficialfor facilitating a closest packing density or for minimizing the timenecessary to obtain such a packing density. Vibrating time may varydepending upon the size of the mold, the average size of the hollowmetallic pieces, the average size of the metal powders, and thefrequency of the vibration. Generally, vibrating can be performed for aperiod of time up to about 12 hours, although longer or shorter timeperiods may be necessary or sufficient. In one particular embodiment,vibrating is performed for a period of time ranging between about 30seconds and about 4 hours, preferably about 1 minute to about 3 hours,more preferably about 5 minutes to about 2 hours.

Similarly, other mechanical means can be used for facilitating packingdensity. Computer modeling could also be used to determine optimumpacking techniques, including establishing sphere sizes most useful foroptimum packing densities in light of mold size and shape. Wherecomputer modeling is used, automated packing of the spheres could bebeneficial for arranging the spheres in a maximized packing density.Further, in embodiments where hollow metallic pieces having anon-spherical geometry are used, different mechanical means could beused for establishing the most efficient packing density of the metallicpieces given their geometries.

Once the hollow metallic spheres have been arranged in the mold, amatrix-forming metal powder is introduced into the mold, filling thespaces around the hollow metallic spheres. Again, mechanical means, suchas vibrating, can be used to facilitate movement of the metal powderaround the hollow metallic spheres, preferentially completely fillingany voids within the mold. Multiple rotations of adding powder andapplying mechanical means to move the powder into the voids betweenspheres within the mold could be used to ensure complete filling of themold. Further, it may be beneficial, particularly when filling largemolds, or molds of complex shape, to alternate introduction of thespheres and the matrix forming powder into the mold to ensure completefilling of the spaces between the hollow metallic pieces.

As previously noted, the metal powder used in the powder metallurgyprocess can comprise various different metals, the metal being the samemetal type or a different metal type as the metal comprising the hollowmetallic spheres. In one embodiment, the composite metal foam compriseshollow steel spheres and aluminum powders. In another preferredembodiment, the composite metal foam comprises hollow steel spheres andsteel powder. Particular, non-limiting examples of materials useful as ametal matrix, according to certain embodiments of the invention, are316L stainless steel, Ancorsteel-1000C steel, and aluminum 356 alloy,the compositions of which are provided in Table 2.

TABLE 2 Exemplary Metal Powder Matrix-Forming Compositions TypeComposition 316L Stainless 0.03% carbon, 0.3% oxygen, 17% chromium, 13%Steel: nickel, 0.9% silicon, 0.2% manganese, 2.2% molyb- denum, andremaining balance iron Ancorsteel- 0.003# carbon, 0.006% phosphorus,0.007% sulfur, 1000C Steel: 0.002% silicon, 0.005% oxygen, 0.003%nickel, 0.02% molybdenum, 0.1% manganese, 0.05% copper, 0.02% chromium,and remaining balance iron Pure 99.9% Al Aluminum:

Choice of metal powder can depend upon the desired physical propertiesof the composite metal foam. Further, choice of metal powder can belimited by such characteristics as particle size and flowcharacteristics. For example, electrostatic interactions can limit theflow of some powder types leading to agglomeration and incompletefilling of the voids between the hollow metallic spheres.

Choice of metal powder can also be limited by chemical and physicalchanges in the matrix material brought about by sintering. For example,it is known that the strength of sintered steel increases withincreasing carbon content, up to about 0.85% carbon (see ASM MetalsHandbook, 9.sup.th Edition, Vol. 7, “Powder Metallurgy”, AmericanSociety for Metals, 1984, which is incorporated herein by reference).Beyond this, a network of free cementite begins to form at the gainboundaries. Additionally, it has been shown that for similar sinteringconditions, shrinkage decreases with increasing carbon content up to 8%,at which no shrinkage was noted (see, N. Dautzenberg, Powder MetallurgyInternational, vol. 12, 1971 and Dautzenberg and Hewing, PowderMetallurgy International, vol. 9, 1977, both of which are incorporatedherein by reference).

Further considerations in choosing the metal matrix-forming powder arisefrom the possible formation of unsuitable intermetallic compounds duringsintering. Such formation can be prevented, to some extent, bycontrolling sintering conditions. For example, when using an aluminumpowder matrix-forming material with hollow steel spheres, diffusion ofmatrix material into the spheres and the formation of a brittleintermetallic phase may occur, particularly with slow process andprolonged exposure of the combination of iron and aluminum at highertemperatures.

The metal powder is preferentially of a particle size capable ofachieving a favorable packing system for maximizing matrix density. Forexample, in one embodiment, aluminum powder is used, the powder being a98% pure mixture of the following components: 75% H-95 Al powder (about100 micron particle size); 14% H-15 Al powder (about 15 micron particlesize); and 11% H-2 Al powder (about 2 micron particle size). Suchpowders are available commercially from vendors, such as Valimet, Inc.(Stockton, Calif.). A powder composition, such as described above, isclose to the ideal 49:7:1 ratio to achieve an optimum trimodal packingsystem for greater matrix density. In another embodiment,Ancorsteel-100.degree. C. iron powder is used. The powder is sieved to81.3%-325 mesh (44 micron) powder and 18.7%-400 mesh (37 micron) powder.Ancorsteel-100.degree. C. powder is commercially available from ARCMetals (Ridgway, Pa.). In further embodiments, powders of an essentiallyuniform particle size, or of various particles sizes, can be used formaximizing matrix density. For example, powders having particle sizesmost favorable for achieving an optimum bimodal packing system couldalso be used.

In one embodiment, the metal powders used as a matrix-forming metalpowder in the invention have an average particle size of about 1 μm toabout 200 μm. Preferably, the metal powder has an average particle sizeof about 10 μm to about 100 μm, more preferably about 15 μm to about 75μm, most preferably about 20 μm to about 50 μm.

Metal powders, such as those described above, can be used alone as thematrix forming metal powder. Alternately, further additional componentscan be combined with the metal powder. For example, in one embodiment ofthe invention, the metal powder further includes carbon in the form of−300 mesh crystalline graphite to further increase the strength of thelow carbon steel matrix, as described above.

Further reinforcement agents can also be added to the metal powder priorto introduction of the powder into the mold. For example, natural orsynthetic fibers or particulate matter could be mixed with the metalpowder, or added into the mold, to provide additional benefits, such asincreased strength or heat resistance.

Once the spaces around the hollow metallic spheres have been filled withthe matrix-forming metal powder, the mold is heated to a sinteringtemperature, the appropriate temperature being dependant upon thecomposition of the powder and the composition of the metallic spheres.Where the metal powder has a sintering temperature well below thesintering temperature of the metallic spheres, the lower temperature maybe used, thereby sintering the metal powder and forming a solid metalmatrix around the hollow metallic spheres. When the metallic spheres andthe metal powder comprise the same metal, or different metals havingsimilar sintering temperatures, the metal powder and, to some extent,the metallic spheres are sintered, thereby forming a solid metal matrixaround the hollow metallic spheres.

In one embodiment, the metal powder is sintered with the contents of themold under pressure, such as in a hot press. Pressure values can varydepending upon the mechanical and physical properties of the spheres.Further, sphere size can also affect the applied pressure range.Acceptable pressure ranges can be calculated based upon the yieldstrength of the hollow sphere and the permissible load that can beapplied to the spheres without any permanent deformation of the spheres.

According to one embodiment, sintering is conducted without applicationof external pressure. In this embodiment, thermal expansion of thespheres during sintering and the resulting localized pressure around thespheres were used to facilitate pressing of the powder into the spacesbetween the spheres. The results show minimal porosity in the matrix ofthe composite metal foam after sintering.

Sintering temperature can vary depending upon materials used in thespheres and, particularly, in the matrix-forming metal powder. In oneembodiment, where hollow steel spheres and aluminum powder are used, thesintering is performed at a temperature of about 630° C. In anotherembodiment, where hollow steel spheres and steel powder are used, thesintering is at a temperature of about 1200° C. Preferably, sintering isperformed at a temperature sufficient to exceed the solidus temperatureof the metal matrix-forming powder but remain below the liquidustemperature of the powder. Further, preferably, the sinteringtemperature does not exceed the solidus temperature of the hollowmetallic spheres. In one particular embodiment, sintering is performedat a temperature of between about 500° C. and about 1500° C., preferablybetween about 550° C. and about 1400° C., more preferably between about600° C. and about 1300° C.

Sintering time can also vary depending upon the materials used in thehollow metallic spheres and the metal matrix-forming powder. Sinteringtime also varies, however, based upon the relative size of the mold (andtherefore the size of the sample being prepared). Larger molds obviouslyrequire a longer sintering time to ensure sintering completely throughthe thickness of the sample. Likewise, smaller molds requires a lessersintering time. Size considerations in relation to sintering timegenerally follow guidelines similar to those previously provided inrelation to powder metallurgy processes.

Sintering conditions are preferably optimized to achieve improvedmechanical properties. In one preferred embodiment, a duplex cycle isused to provide improved mechanical properties due to differentsintering mechanisms taking place at each temperature. Such a methodgenerally comprises cycling temperature increase phases with temperaturehold phases. In one particular embodiment, where a composite metal foamis prepared using steel spheres and steel powder, the sample is heatedat 10° C./minute, held for 30 minutes at 850° C., heated at 5°C./minute, held for 45 minutes at 1200° C., and cooled to roomtemperature at 20° C./minute. In such cycles, the lower temperatureportion assists in the removal of oxides and impurities and helps bringthe mold to thermal equilibrium to avoid gradient properties. Surfacetransport effects are most prevalent at lower temperature, so the bondsbetween particles are strengthened without densification of the matrix.At higher temperatures, strength is increased greatly as a result of thehigher sintering rate due to greater atomic motion. For bothtemperatures, rapid increases in strength are noted for times up to 30minutes, where the rate begins to decrease.

FIG. 2 provides an optical, cross-sectional image of a hollow metallicfoam according to the invention prepared by powder metallurgy usinghollow steel spheres of 3.7 mm average diameter and a sintered steelpowder matrix. FIGS. 3 and 4 provide scanning electron microscopy (SEM)images of a composite stainless steel foam prepared using a powdermetallurgy technique, as described above. FIG. 3 shows the cross-sectionof intact spheres, and FIG. 4 shows the sintered powder matrixcompletely filling the space between the spheres. The bonding betweenthe spheres and the matrix is seen to be strong with no voids at theinterface.

Returning to FIG. 2, the hollow metallic spheres show some signs ofuniform packing; however, it is desirable to further increase theuniformity and density of the packing of the spheres to create compositemetal foams exhibiting more uniform properties and even lower densities.The benefits of improving uniformity and density of packing are furtherillustrated in FIGS. 5 and 6.

FIG. 5 provides a SEM image of a cross-section of two spheres in contactwith one another. FIG. 6 provides a SEM image of a cross-section of twospheres not in contact, but with the metal matrix filling the spacebetween the spheres. Increasing packing density of the spheres increasesthe contact between the spheres reducing the amount of free spacebetween the spheres. Consequently, increased packing density reduces theamount of metal matrix present in the foam, which generally leads tolower densities, without sacrificing strength. FIGS. 5 and 6 furtherillustrate the ability to reduce the density of the composite metal foamby using hollow metallic spheres having lesser wall thicknesses. This isparticularly illustrated in FIG. 5, wherein the sphere in the lowerportion has a noticeably thinner wall than the sphere in the upperportion of the figure. The presence of the metal matrix surrounding thehollow metallic spheres allow for reducing the wall thickness to lowerdensity of the composite metal foam without sacrificing strength.

According to another embodiment of the invention, there is provided amethod for preparing a composite metal foam by casting. In oneembodiment, which is described below, the composite metal foam isprepared by permanent mold gravity casting; however, various othercasting methods, as would be recognizable by one of skill in the art,could be used. Accordingly, the present invention is not limited by thepermanent mold casting method described herein but rather encompassesall casting methods that could be recognizable as useful.

In one embodiment of a casting method according to the invention, thehollow metallic spheres are first placed inside the mold. The hollowspheres are preferably arranged inside the mold, such as throughvibrating, to pack the spheres into a best attainable close packeddensity. Vibration methods and apparatus, as described above in relationto powder metallurgy methods, would also be useful according to thisaspect of the invention. Once the spheres are packed in the mold, amatrix-forming liquid metal is cast into the mold, filling the spacesaround the hollow metallic spheres. The liquid metal is then solidifiedto form a solid metal matrix around the hollow metallic spheres.

One embodiment of a mold useful in the casting method of the inventionis illustrated in FIGS. 7 and 8, which show a three-dimensional view anda cross-sectional view, respectively, of an open atmosphere gravity feedpermanent mold. The mold incorporates a sprue, runner, melt filter, andoverflow riser. Carbon steel is a particularly preferred material forthe mold allowing for repeated exposure to molten metal and highpre-heating temperatures.

In a mold, such as shown in FIGS. 7 and 8, liquid metal is poured intothe sprue. The liquid metal then travels through the runner, rises upthrough a slide gate and melt filter, fills the spaces between thehollow metal spheres, and flows up into the over-flow riser. Such a“bottom-up” filling approach allows the liquid matrix-forming metal topush out the air as the metal fills the interstitial space between thehollow metallic spheres. The slide gate allows for easy de-molding aftersolidification, and the melt filter serves to remove any solidimpurities or oxides in the melt. The overflow riser feeds any shrinkageduring aluminum solidification.

In one particular embodiment, prior to introduction of thematrix-forming liquid metal, the mold and hollow spheres are pre-heated.Preferably, the pre-heat temperature is at least about equal to thecasting temperature of the matrix-forming liquid metal. For convenience,the matrix-forming metal can be liquefied in the same furnace used forpre-heating the mold and spheres. The temperature of the mold andspheres should be at least about equal to the casting temperature of thematrix-forming liquid metal in order to prevent premature solidificationof the matrix before complete filling of the mold, including the spacesbetween and around the spheres. The pre-heat temperature can be greaterthan the casting temperature of the matrix-forming liquid metal so longas the temperature does not approach the solidus temperature of thespheres.

In this method, the hollow metallic spheres and the matrix-forming metalcomprise different metal compositions, the compositions beingdistinguished by a difference in their melting temperatures. Since thematrix-forming metal is introduced to the mold in a molten state, it isnecessary that the hollow metallic spheres comprise a metal compositionhaving a melting temperature greater than the melting temperature of thematrix-forming metal composition. This avoids the possibility of meltingof the hollow metallic spheres during pre-heating or during introductionof the matrix-forming liquid metal melting into the mold.

Where the metal compositions comprise essentially pure single metals,the transition from solid to liquid generally can be described as asingle melting temperature. Where metal mixtures are used, however, thestate transition becomes more complex and can be described withreference to the solidus temperature and the liquidus temperature. Whenan alloy is heated, the temperature at which the alloy begins to melt isreferred to as the solidus temperature. Between the solidus and liquidustemperatures, the alloy exists as a mixture of solid and liquid phases.Just above the solidus temperature, the mixture will be mostly solidwith some liquid phases therein, and just below the liquidustemperature, the mixture will be mostly liquid with some solid phasestherein. Above the liquidus temperature, the alloy is completely molten.

The metal composition used as the matrix-forming liquid metal of theinvention should have a melting point (or a liquidus temperature) thatis below the melting point (or solidus temperature) of the metalcomposition comprising the hollow metallic spheres. Preferably, themelting temperature of the matrix-forming liquid metal is at least about25.degree. C. less than the solidus temperature of the metal compositioncomprising the hollow metallic spheres, more preferably at least about40° C. less, most preferably at least about 50° C. less than the solidustemperature of the metal composition comprising the hollow metallicspheres.

In one embodiment, the hollow metallic spheres are comprisedpredominately of steel and the matrix-forming liquid metal is aluminumor an aluminum alloy. For example, the hollow metallic sphere couldcomprise low carbon steel or 316L stainless steel, such as according tothe compositions exemplified in Table 1. Likewise, the matrix-formingliquid metal could comprise aluminum 356 alloy, such as according to thecomposition exemplified in Table 2. Aluminum 356 alloy is particularlyuseful due to its low density, high strength and stiffness, and ease ofcasting of the material.

Further reinforcement agents can also be added to the matrix-formingliquid metal prior to casting. For example, natural or synthetic fibersor particulate matter could be mixed with the liquid metal, or addedinto the mold, to provide additional benefits, such as increasedstrength or heat resistance.

Preferentially, the matrix-forming liquid metal is cast into the mold insuch a manner as to facilitate complete filling of the voids around thehollow metallic spheres while avoiding disturbance of the hollowmetallic spheres arranged within the mold. In some embodiments, it maybe useful to use screens, or other similar means, for maintaining thearrangement of the spheres within the mold. In addition to gravitycasting, the mold may be subject to pressure differentials during thecast process. For example, in one embodiment, the mold may bepressurized. In another embodiment, the mold may be under a vacuum.

Once the matrix-forming liquid metal has been cast into the mold, theliquid metal is solidified to form a solid metal matrix around thehollow metallic spheres. Such solidification is generally throughcooling of the mold, which can be through atmospheric cooling or throughmore controlled cooling methods.

A composite metal foam, according to one embodiment of the invention,prepared by casting an aluminum metal matrix around hollow low carbonsteel spheres, is shown in FIG. 9. As can be seen in the figure, theclosest packing arrangement of the hollow spheres is somewhat disturbedby the inflow of the liquid metal matrix. Nevertheless, strong bondingbetween the metal matrix and the hollow spheres is achieved.

Bonding between the foam components is more clearly evident in FIGS.10-11 which provide SEM images of a cast, composite metal foam accordingto the invention comprising hollow low carbon steel spheres surroundedby an aluminum metal matrix. As can be seen in FIG. 10, the aluminummetal matrix fills the interstitial space between the hollow steelspheres with consistent bonding to the surfaces of the spheres. FIG. 11provides a detailed view of the sphere wall interaction with thealuminum matrix. Very little evidence of influx of aluminum matrix intothe walls of the hollow steel spheres is seen in FIG. 11 indicating lowporosity in the wall of the hollow steel spheres.

SEM images of a cast, composite metal foam according to anotherembodiment of the invention are provided in FIGS. 12(a) and 12(b). Whileit is preferable for the interstitial space between the spheres to becompletely filled by the metal matrix, as can be seen in FIG. 12(a),voids can be present, particularly at an interface between two spheres.Using geometrical calculations, the void space at the interface of twospheres can be calculated according to an estimated void angle, and theresulting void volume (V_(void)) per contact point of two spheres can becalculated according to the following equation:

V _(void)=3.16×10⁻²(R ³)  (1)

in which R is the outer radius of the spheres used in the foam (seeSanders, W. S, and Gibson, L. J., Mater. Sci. Eng. A A347, 2003, p.70-85). Projecting this into a face-centered cubic (FCC) arrangement ofspheres with four spheres per unit cell, and knowing that in a randomloose condition, there are three contacts per unit cell, the totalvolume percentage of voids per unit cell can be estimated as:

V _(fv)=(3.16×10⁻² R ³12)/22.627R ³  (2)

in which V_(fv) is the volume fraction of voids. In one particularcomposite metal foam according to the invention prepared by castingmolten aluminum around hollow low carbon steel spheres, the volumepercentage of voids calculated according to equation (2) was 1.68%.However, the actual matrix porosity is expected to be even less, giventhere are less than four spheres in each unit cell of the randomarrangement and not all contacts have a void space. In one embodiment ofthe invention, the void volume percentage is less than 1.5%, preferablyless than 1.25%, more preferably less than 1%.

As can be seen in FIG. 12(b), multiple different phases are present inthe aluminum matrix. Scanning electron microscope energy dispersivex-ray spectroscopy (SEM EDX) compositional analysis was performed on anAl—Fe composite metal foam according to one embodiment of the inventionprepared by casting, and the compositional analysis is provided below inTable 3.

TABLE 3 Compositional Analysis (atomic %), t = trace Al Si Fe Mg Mn CuAl matrix generally 97.9 1.5 t t t T Light gray phase 65-75 10-20 15-25t 3.5 1.9 Dark gray phase 97.1 ≦3 t t t 1.0

As can be seen in FIG. 12 and Table 3, the Al matrix typically comprisesthree different phases. The Al matrix generally comprises approximately98% Al. The phase designated the light gray phase is a ternary alloy ofAl, Si, and Fe (estimated to be Al.sub.4FeSi) and is typically found intwo different shapes, plates and needles. The phase designated the darkgray phase has a composition that is close to the composition of the Almatrix generally but also includes copper.

The composite metal foams of the invention (whether prepared throughcasting or powder metallurgy) are particularly characterized in thatthey exhibit high compressive strength and energy absorption capacitywhile maintaining a relatively low density. Of course, actual density ofthe finished composite metal foam can be calculated using the measuredsample weight and structural dimensions. It is also possible, however,to determine an estimated density based on component properties andpacking properties of the spheres in the mold.

Sphere packing density is a measure of the relative order of thearrangement of spheres, such as in a mold. It is desirable to achieve amaximum density of spheres in order to maintain a lowest possibledensity for the prepared composite metal foam and have a uniformdistribution of spheres, thus contributing to isotropy of mechanicalproperties. It is generally recognized that there are three types ofpacking arrangements for spheres: ordered packing, random dense packing,and random loose packing (See, German, Particle Packing Characteristics,Metal Powder Industries Federation, Princeton, N. J., 1989). The highestorder is represented by the face-centered cubic (FCC) or hexagonalclosed packed (HCP) structure, with a 74% packing density of spheres,assuming mono-sized spheres. A random dense arrangement has a packingdensity of 64%. This is achieved by vibrating an initially randomarrangement to the best attainable packing density. Random loose packinghas a fractional density of 56%-62.5%, with an average reported fractiondensity of 59% and a three-point contact per sphere.

As previously noted, in one preferred embodiment of the invention, afterthe hollow metal spheres are loaded into a mold (in either a casting orpowder metallurgy technique), the mold with the spheres is vibrated toachieved increased packing density, which ultimately leads to reducedoverall density for the prepared composite metal foam of the invention.In one test, hollow spheres were poured in bulk into an acrylic box.Isopropyl alcohol was then poured into the box as a testing replacementfor the matrix material to determine the volume needed to fill the box.With this random placement, sphere packing density was measured as 56%.In a second run, the spheres were manually vibrated prior tointroduction of the isopropyl alcohol. The vibrated spheres exhibited apacking density of 59%.

The density of a composite metal foam according to the invention can beestimated as a function of component density according to the followingequation:

ρ_(CF)=ρ_(s) V _(fs)+ρ_(m) V _(fm)  (3)

in which ρ_(CF) is the density of the composite metal foam, ρ_(s) is thedensity of spheres, V_(fs) is the volume fraction of spheres (thepacking density of the spheres), ρ_(m) is the density of the matrix, andV_(fm) is the volume fraction of the matrix. Considering the effect ofporosity in the wall thickness of metal spheres, equation (3) can bealtered to:

ρ_(CF)=ρ_(metal)[1−(V _(in) /V _(out))]V _(fs)(1−V _(fp))+ρ_(m) V_(fm)  (4)

in which ρ_(metal) is the density of the metal used in the hollow metalspheres (e.g., steel), V_(in)/V_(out) is the ratio of inner volume toouter volume of the metal spheres, and V is the volume fraction ofporosities in the wall thickness. As previously noted, the porosity ofthe walls of the hollow metal spheres can vary and is preferably lessthan about 12%.

As previously noted, the composite metal foams of the invention areparticularly useful in that they provide a material that combinesstrength with light weight. In particular, the composite metal foamsgenerally have a density that is less than the density of the bulkmaterials used in the composite metal foams. For example, steel isgenerally recognized as having a density in the range of about 7.5 g/cm³to about 8 g/cm³. A composite metal foam prepared according to thepresent invention using hollow steel spheres and a steel metal matrixwould exhibit a density well below these values.

The composite metal foams according to the present invention preferablyhave a calculable density of less than about 4 g/cm³. Preferably, thecomposite metal foams of the invention have a density of less than about3.5 g/cm³, more preferably less than about 3.25 g/cm³, and mostpreferably less than about 3.0 g/cm³. In one embodiment of theinvention, there is provided a composite metal foam comprising hollowsteel spheres surrounded by an aluminum metal matrix, the composite foamhaving a density of less than about 2.5 g/cm³. In another embodiment ofthe invention, there is provided a composite metal foam comprisinghollow steel spheres surrounded by a steel metal matrix, the compositefoam having a density of less than about 3.0 g/cm³.

The composite metal foam of the invention can also be evaluated in termsof relative density. By analysis of this parameter, it is possible tocompare the level of porosity of the composite metal foam (or the levelof foaming) with the level of porosity of the bulk material. Accordingto one embodiment of the invention, the inventive composite metal foamhas a relative density (compared to bulk steel) of between about 25% andabout 45%.

The usefulness of the composite metal foams according to the inventionis particularly characterized by the favorable strength to density ratioof the foams. As used herein, strength to density ratio is determined asthe plateau stress of the composite metal foam under compression(measured in MPa) over the density of the composite metal foam. Thecomposite metal foams of the invention typically exhibit a strength todensity ratio of at least about 10. Preferably, the composite metalfoams of the invention can exhibit a strength to density ratio of atleast about 15, more preferably at least about 20, still more preferablyat least about 25, and most preferably at least about 30.

The inventive composite metal foams particularly can exhibit a strength,evaluated as the plateau stress, of at least about 25 MPa, at leastabout 30 MPa, at least about 35 MPa, at least about 40 MPa, at leastabout 50 MPa, at least about 75 MPa, or at least about 100 MPa.

The composite metal foams of the invention are further characterized bytheir improved energy absorption. Energy absorption capability can becharacterized in terms of the amount of energy absorbed by the compositemetal foam over a given level of strain. As used herein, energyabsorption is defined as the energy absorbed (in MJ/m³) up to 50%strain. The composite metal foams of the invention typically exhibitenergy absorptive capability of at least about 20 MJ/m³. Preferably, thecomposite metal foams of the invention exhibit energy absorptivecapability of at least about 30 MJ/m³, more preferably at least about 50MJ/m³, most preferably at least about 75 MJ/m³.

As detailed above, the composite metal foams of the invention arefurther particularly beneficial in that they provide improved mechanicalproperties under cyclic compression loading. Further, microstructural,mechanical, and physical properties show noticeable improvement overprevious metal foams through analysis by optical microscopy, scanningelectron microscopy (SEM), energy dispersive X-ray analysis (EDX), andcompression test and strain mapping during monotonic compressionloading.

Any method or apparatus recognizable as useful by one of skill in theart for obtaining and analyzing the above-noted properties could be usedand is fully envisioned by the present invention. For example, SEMimages can be obtained through use of a Hitachi S-3200N environmentalSEM equipped with energy dispersive X-ray spectroscopy. Of course, otherSEM equipment, as would be recognized as suitable by the skilledartisan, could also be used in accordance with the invention.

One particular method of analysis of the mechanical properties of thecomposite metal foams according to the invention is through monotoniccompression testing and compression fatigue testing. Exemplary equipmentuseful in such testing is a MTS 810 FLEXTEST™. Material Testing System(available from MTS Systems Corporation). According to one testingprocedure, monotonic compression testing is performed using a MTS 810loading machine with a 220 kip load cell. According to another testingprocedure, compression fatigue testing is performed using a MTS 810loading machine with a 220 kip load cell having a fixed R-ratio(R=σ_(min)/σ_(max)) of 0.1 at a frequency of 10 Hz and an appliedmaximum stress of 37.5 MPa.

FIG. 13 provides a side-by-side comparison of three foams preparedaccording to the invention. FIG. 13(a) is a cross-section of cast,composite metal foam comprising hollow low-carbon steel spheres (3.7 mmmean diameter) and an aluminum matrix. FIG. 13(b) is a cross-section ofa composite metal foam prepared by powder metallurgy comprising hollowlow-carbon steel spheres (3.7 mm mean diameter) and a metal matrixprepared from powdered low carbon steel. FIG. 13(c) is a cross-sectionof a composite metal foam prepared by powder metallurgy comprisinghollow low-carbon steel spheres (1.4 mm mean diameter) and a metalmatrix prepared from powdered low carbon steel.

Monotonic compression testing of all three samples from FIG. 13demonstrated the typical behavior of an elastic-plastic foam undercompression. There is an initial linear elastic region, which isfollowed by an extended region of deformation at a relatively constantlevel of stress. Unlike most foams, however, the foams preparedaccording to the present invention do not exhibit a level plateaustress. Rather, the material densifies at a slowly increasing rate, andthere is no distinct point at which full densification occurs. As usedherein, plateau stress is understood to refer to the average stressbetween the yield point and the point at which 50% strain (i.e.,deformation) has been achieved. All three composite metal foams shown inFIG. 13 reached a minimum of 50% strain before reaching a point of fulldensification.

FIG. 14 shows stress-strain curves of composite metal foams according tovarious embodiments of the invention under monotonic compression. Sample1 is taken from an embodiment formed through powder metallurgy using 3.7mm hollow low carbon steel spheres and low carbon steel powder. Sample 2is taken from an embodiment formed through casting an aluminum matrixaround 3.7 mm hollow steel spheres. Sample 3 is taken from an embodimentformed through powder metallurgy using 1.4 mm hollow low carbon steelspheres and low carbon steel powder. Sample 4 is taken from anembodiment formed through powder metallurgy using 2.0 mm hollowstainless steel spheres and stainless steel powder. After 50% strain,the composite metal foams begin to approach densification as the hollowspheres are completely collapsed and the material begins to heave like abulk material.

The compression test results, as well as further physical properties ofthe embodiments of the inventive composite metal foam corresponding tothe four samples discussed above in relation to FIG. 14, are shown belowin Table 4. As a comparative, the physical properties of previouslyknown metal foams made of hollow spheres alone are also provided.Comparative HSF 1 is a steel foam described by Anderson, O., Waag, U.,Schneider, L., Stephani, G., and Kieback, B., (2000), “Novel MetallicHollow Sphere Structures”, Advanced Engineering Materials, 2(4), p.192-195. Comparative HSF 2 is also a steel foam described by Lim, T. J.,Smith, B., and McDowell, D. L. (2002), Behavior of a Random HollowSphere Metal Foam”, Acta Materialia, 50, P. 2867-2879.

TABLE 4 Sam- Sam- Sam- Sam- HSF HSF ple 1 ple 2 ple 3 ple 4 1 2 SphereOD (mm) 3.7 3.7 1.4 2.0 2-3 2 Sphere wall thickness (mm) 0.2 0.2 0.05.01 0.25 0.1 Density (g/cm³) 3.2 2.4 2.7 2.9 1.4 1.4 Relative Density(%) 40.7 42 34.2 36.8 — — Plateau Stress (MPa) 42.3 67 76 136 23 4.8Densification Strain (%) 55 50 50 50 60 65 Strength/Density Ratio 13.228 29.5 47 16 4 Energy Absorbed up to 21 32.3 37.6 68 — — 50% strain(MJ/m³)

Samples 1 and 3 above are powder metallurgy foams comprising low carbonsteel. Sample 2 is a cast Al—Fe foam. Sample 4 is a powder metallurgyfoam comprising stainless steel. The comparison in Table 4 indicates thecomposite foams of the invention have a noticeably increased strengthwhile maintaining a comparable strength to density ratio. Further, theinventive composite foams show improved energy absorptive propertiesmaking the composite foams particularly useful in the variousapplications described herein.

The composite metallic foams of the invention can be useful in forming avariety of structure and material where improved material properties,such as high strength and/or low density, and/or high energy absorption,are desirable. Such properties make the inventive composite metal foamsparticularly useful for articles that can provide protection to objectsor individuals against potentially damaging or injury causing events.

For example, the inventive metallic foams can be particularly useful inthe construction of various components of aerospace vehicles. Suchvehicles, whether for air travel or space travel, can suffer damage andeven catastrophic failure due to impact from other bodies. Specifically,airplanes can be subject to damage from bird strikes, particulate matterin the air, and other flying objects. Accordingly, it can be useful toutilize a composite metal foam according to the present invention as acomponent of the structure of an airplane. Specifically, the compositemetal foam can be used as a component of a jet engine, particularly ajet engine fan blade or an airplane propeller. Bird strikes, inparticular, can cause catastrophic failure of airplane enginecomponents, and the use of the inventive composite metal foams cansubstantially stop such failures in light of the energy absorptionnature of the materials. The composite metal foams likewise can be usedin body components of an airplane, particularly in the nose cone and theleading wing edges, which body areas can be particularly susceptible todamage from bird strikes or the like. The high strength composite metalfoams with their excellent energy absorption characteristics, however,can reduce or eliminate damage from such strikes, and the relatively lowdensity of the materials can allow for such protection withoutsignificantly increasing the weight of the airplane. The composite metalfoams also can be useful in the landing components of aerospacevehicles. For example, the landing gear of an airplane can incorporatethe composite metal foam to increase the energy absorption of thestructural components. Likewise, the landing skids of helicopters canincorporate the composite metal foams, which can actually replace themuch costlier titanium construction presently used in many such skids.

The composite metal foams of the invention can find particular use inspace vehicles, including manned and unmanned vehicles. Space vehiclesare susceptible to a variety of high energy challenges, includingradiation, kinetic energy (such as from space debris and micrometeroidimpact), and temperature extremes. Thus, the composite metal foams ofthe invention can be particularly useful in components, such as bodycomponents, of space vehicles. As more fully described below, thecomposite metal foams can be combined with further materials to providestructures that exhibit excellent impact resistance, thermal protection,and radiation protection.

Structures that incorporate composite metal foams according to theinvention also can extend into the realm of civil engineering.Specifically, heavy structures, such as buildings, can include thecomposite metal foams into a variety of their components to provide highstrength components that also are relatively light weight and that alsoprovide high energy absorption. Thus, the composite metal foams can finduse in building framing and other supports, walls, and floors. Evenfurther, the composite metal foams can be used in shock absorbing bracesfor buildings. Such braces can be particularly useful in theconstruction of buildings in areas susceptible to earthquakes. Forexample, the composite metal foams can be sandwiched between other bracecomponents in a movable arrangement such that the braces can lengthenand shorten with the movement of the ground during an earthquake, andthe composite metal foams can absorb the energy in the compressive phaseto reduce shock to the remaining building components. The compositemetal foams thus can be utilized as an efficient and low cost passiveisolation system for seismic protection, and such systems can beretrofitted to existing structures as well as implemented in newconstruction.

In still further embodiments, structures incorporating the compositemetallic foams can include automobiles (or other vehicles, such astrucks, buses, trains, etc.). For example, most automobiles include acrash box (or crumple zone) formed of materials that are intended toabsorb impact in a crash. The crash box may include an impact beam(e.g., a bumper). Current standards for automotive bumpers only requireprotection of auto body in collisions of 2.5 mph (4 km/h). Compositemetal foams according to the invention, however, can provide excellentresults in collisions up to much higher speeds. The inventive compositemetal foam's low weight and good energy absorbing properties can makethe composite metal foam useful in construction of a variety ofcomponents for moving vehicles, including all structural components,particularly components of the crumple zones in automobiles (i.e., useas shock absorbing components of the vehicles).

The application of the inventive composite metal foams can also beextended into biomedical engineering as medical implants. Specifically,the composite metal foams can be utilized in any medical or dentalstructure where the physical properties of the foams significantly matchproperties of the body. In particular, the composite metal foams can beused in structures designed for bone implant.

Bone implants can be particularly useful for replacing or improving bonequality in areas of bone damage, such as injury, disease, abnormaldevelopment, or wear (e.g., arthritis). Materials typically used forbone implants are metallic materials, such as stainless steel, cobaltbased alloys, and titanium based alloys. Stainless steel implants havereasonable corrosion resistant and biocompatibility with high strengthand ease of production while maintaining a low cost. Co—Cr alloys offervery good corrosion resistance but they are brittle and difficult tofabricate. Titanium and its alloys are of particular interest forbiomedical applications because of their outstanding biocompatibility,as well as their tendency to exhibit little or no reaction with tissuesurrounding the implant. Titanium also exhibits the lowest densitycompared to the other noted classes of biomaterials, and that makes itmore attractive as a bone replacement. This is mainly because boneitself has a relatively a low density, and a bone replacement ideallywill match its density to maintain the distribution of body weight inbalance. The average bone density is about 1.5 g/cc while the density ofsteel, cobalt, and titanium are 7.8, 8.9 and 4.5, respectively. Of thematerials already known for use in bone replacement therapies, titaniumalloys thus appear to provide the closest density to bone.

Stiffness, modulus of elasticity, or moduli of biomedical implants(which relate to the tendency of a material to be deformed elastically(non-permanently) under loading) also must be considered in choosing asuitable bone replacement material. Known bone implants exhibit astiffness or modulus of elasticity that is significantly greater thanthe stiffness/modulus of bone, and this discrepancy causes the metallicdevices implanted in the body to take a disproportionate share of thestructural load in the area of the implant. Consequently, the actualload experienced by bone will be proportionally lower due to thephenomenon known as “stress shielding”. Stress shielding refers to thereduction in bone density as a result of removal of normal stress (load)from the bone by an implant. This is explained by Wolff s law thatstates: “the bone in a healthy person or animal will adapt to the loadsit is placed under.” If loading on a particular bone increases, the bonewill remodel itself over time to become stronger to resist that sort ofloading. In turn, if the loading on a bone decreases, the bone willbecome weaker since there is no stimulus for continued remodeling thatis required to maintain bone mass. In other words, natural bone needsloads applied to it on a regular basis in order to maintain a normal,healthy state.

Titanium and its alloys typically exhibit a moduli of about 105 to about125 GPa. Steel has a moduli of around 205 GPa, and cobalt alloys have amoduli of about 240 GPa. On the other hand, natural bone has an averagemodulus of elasticity of about 17 GPa (i.e., in the range of about 7 GPato about 30 GPa generally, depending upon the age and health conditionof the individual). As the result, titanium alloys have become the mostpopular implant alloys due to their closest moduli to that of bone andthe less potential to stress shielding. This is despite of the fact thatTi implants are pricier than stainless steel implants. Titanium is arelatively dense material and, in some case, in order to achieve abetter property, a layer of a porous material can be coated on theoutside of a titanium implant to improve osseointegration. This,however, can increase the price of the implant even higher and doeslittle or nothing to lessen the stiffness discrepancy between theimplant and the surrounding bone.

In light of the above, orthopedic and dental devices and implantscurrently in use suffer from two main shortcomings. First, the modulusof elasticity of the current implants (as low as about 105 GPa fortitanium materials and high as about 240 GPa for cobalt materials) ismany times higher than that of the surrounding bone. This can causestress shielding, failure of the implant, and the need for revisionsurgery. The stress shielding phenomenon, which leads to deteriorationof bone quality, decrease of bone thickness, decrease of bone mass, andosteoporosis (bone resorption), and these phenomena can loosen aprosthetic device and lead to revision surgery. Second, current implantshave a density that is about three times higher than the average densityof natural bone. As the implant presses against the surrounding (lessdense) bone under gravity and during daily life loading, bonedeformation can occur, the implant again can loosen, and implant failurecan again lead to the need for revision.

The composite metallic foams of the present invention can be effectiveas bone implants that can reduce failure rates and substantially improveimplant function and its lifetime in the body. This is because thecomposite metal foams can provide optimized density and substantiallyimproved mechanical and biomedical properties. In particular, theinventive composite metal foams desirably mimic the density and elasticmodulus of natural bone. Beneficially, the composite metal foam can bemade out of stainless steel, cobalt, chromium, and/or titanium and canbe formed with desirable porosities that likewise significantly mimicthe porosity of natural bone. The composite metal foams can provide highstrength and fracture toughness, low density, and the ability to tailorthe modulus of elasticity to that of a patient's natural bone.

In specific embodiments, a composite metal foam according to theinvention can exhibit a modulus of elasticity of less than 75 GPa, lessthan 50 GPa, less than 40 GPa, or less than 30 GPa. In specificembodiments, the composite metal foam can exhibit a modulus ofelasticity of about 5 GPa to about 75 GPa, about 7 GPa to about 50 GPa,or about 10 GPa to about 40 GPa. In one embodiment, the modulus ofelasticity of a stainless steel composite metal foam is about 10 GPa toabout 15 GPa. The bone implants of the invention can exhibit a modulusof elasticity that is within about 150%, within about 125%, within about100%, within about 75%, within about 70%, within about 60%, or withinabout 50% of the average modulus of elasticity of natural bone. In otherembodiments, the inventive implants can have a modulus of elasticitythat is within about 150%, within about 125%, within about 100%, withinabout 75%, within about 70%, within about 60%, or within about 50% ofthe of the modulus of elasticity of the natural bone of the subjectreceiving the implant.

It is notable that the density of the composite metal foam can be abouta third of the density of the bulk material from which the compositemetal foam is made. For example, the density of a stainless steelcomposite metal foam according to one embodiment of the invention isabout 2.6-2.7 g/cc, which is substantially close to the density of bone(about 1.5 g/cc). Thus, the inventive metallic foams can becharacterized in regards to their densities relative to bone.Specifically, the inventive composite metal foams can have a densitythat is less than three times the average density of natural bone, thatis less than 2.5 times the average density of natural bone, or that isless than 2 times the average density of natural bone.

The inventive metallic foams can be particularly characterized inrelation to the porosity of the material. In particular, the compositemetal foams can be functionally graded in porosity. By this is meantthat the composite metal foam implant can have porosity that changesacross a dimension of the material. For example, a bone implant can becharacterized in cross-section as having two opposing outer edgesseparated by a defined thickness of the implant. Across this thickness,the porosity can be a first value at one outer edge, increase ordecrease moving toward the approximate center (or middle) of theimplant, and then increase or decrease (or remain substantiallyunchanged, if desired) moving from the approximate center of the implantto the opposing outer edge of the implant. In specific embodiments, theporosity of the implant can be less at the outer edge of the implantthan in the middle of the implant. Porosity can be evaluated in terms ofthe dimensions of the hollow metallic spheres used in preparing thecomposite metal foam. Specifically, the use of spheres of largerdiameter provide a composite metal foam with a greater porosity, and theuse of spheres of smaller diameter provide a composite metal foam with alesser porosity. Thus, porosity can be defined in regard to the averagepore diameter at the defined location within the implant. In certainembodiments, the average diameter of the hollow metallic spheres canincrease from the outer edge of the implant to the middle of the implant(i.e., a greater porosity at approximately the middle of the implant anda lesser porosity at the outer edge of the implant). The porous natureof the composite metal foam of the invention can help in anchoring animplant made therefrom into the surrounding tissue and maintaining astrong bond between the implant and tissue. This can increase thesuccess of orthopedic and dental implantation, cutting back the need forrevision surgery, saving time and money, and lowering the pain forpatients receiving the implants.

It is notable that currently there are some porous coatings used on thesurfaces of some known solid implants in order to decrease the density,improve the bonding to surrounding bone, and lower the stress shieldingeffect. The process of manufacturing such implants, however, requiresmore steps, the produced implant can be costlier, and delamination canoccur between various layers of such implants. Moreover, such effortsstill do not adequately address the stress shielding effect in knownmetallic implants. Additionally, it is important to note that thestructure of natural bone structure is mostly low density in the insideand high density on the outside (i.e., porosity increases moving fromthe outer edge of the bone to the middle of the bone). Known implantsthat incorporate a porous coating, however, provide an implant ofopposing structure. Specifically, such implants have a high density bulkmetal at the core and a low-density, porous layer at the outsidesurface. This construction can decrease the performance of the knownimplants under various types of mechanical loadings. Thus, the compositemetallic foams of the present invention can be particularly useful asbone implants in a wide array of uses. This is because the inventiveimplants can exhibit a functionally graded porosity that issubstantially identical to that of natural bone, can provide a lowdensity this is significantly closer to the average density of naturalbone than known implants, and can effectively overcome stress shieldingin light of the modulus of elasticity that closely matches that ofnatural bone.

In addition to implants, the structures provided according to theinvention that incorporate a composite metallic foam as described hereincan include tools, particularly medical or dental tools. For medical anddental devices used outside of the body (such as knives and tools usedin the surgery room and dentist clinic), the extra weight of the devicemade mostly out of stainless steel is a burden for the surgeon ordentist specially in the long run. The present composite metal foams areparticularly beneficial in the construction of such tools in that theformed tools are lighter yet retain the strength required for suchtools. The composite metal foams particularly may be used in forming thehandles of a variety of tools.

In addition to the foregoing, the composite metal foams of the inventioncan find particular use in a variety of structures in light of theenergy absorption characteristics of the composite metal foams. Thecomposite metal foams can particularly be useful in protective materials(specifically in military uses) to protect against blasts or other shockor projectile injuries. The composite metal foams are particularlyuseful in various types of armors in light of the light weight, highstrength, high energy absorption and excellent fatigue properties. Theproperties provide the composite metal foams with highly usefulballistic properties. For example, the composite metal foam particularlycan be used as vehicle armor, such as in combination with a ceramiclayer. The armored vehicles can be referred to as having blast panels,ballistic panels, or armor panels incorporated therein or includedthereon.

The composite metal foams of the invention can be used alone in theformation of energy absorbing materials. In certain embodiments,however, the invention can provide energy absorption panels thatcomprise a plurality of layer of different material, at least one layerincluding a composite metal foam as discussed herein. As such, theenergy absorption panels can be particularly useful in the preparationof personal protection articles, such as headgear, body armor, andfootwear.

In certain embodiments, the energy absorption panels can be used in bodyarmor. For example, the inventive composite metallic foam can becombined with one or more further layers to provide an armor that islight weight and that can effectively absorb the energy of a projectileand prevent the projectile from passing completely through the armor.

An energy absorbing panel according to the invention specifically caninclude a ceramic layer combined with the composite metal foam layer.Any ceramic material useful in forming body armor or vehicle armor canbe used according to the invention. For example, the ceramic layer canbe formed from oxides (e.g., alumina, beryllia, ceria, and zirconia) aswell as non-oxides (e.g., carbides, borides, nitrides, and silicides).One specific example is silicon nitride (Si₃N₄).

An energy absorbing panel according to the invention also can include apolymer layer combined with the composite metal foam layer. Preferably,such polymer layers are formed of materials providing high strength,such as ultra high molecular weight polyethylene.

An energy absorbing panel according to the invention further can includea cloth layer combined with the composite metal foam layer. Such clothlayers can be made from fibers of a natural material, fibers of asynthetic material, or both. Fibers of ultra high molecular weightpolyethylene, for example, may be used. In preferred embodiments, thecloth layer may be formed of aramid fibers.

In particular embodiments, an energy absorbing panel can comprise alayer including a composite metal foam as described herein sandwichedbetween a ceramic layer and a cloth layer or polymer layer. Panels ofsuch construction can be particularly useful in forming personalprotection articles, such as body armor, because of the excellentability to effectively absorb the energy of projectiles hitting thepanels at high velocity. Specifically, the ceramic layer can be anteriorto the composite metal foam layer (relative to an individual wearing thearmor), and the cloth or polymer layer can be posterior to the compositemetal foam layer (relative to the individual wearing the armor). Suchcan apply to vehicle armors as well.

Another example of a personal protection article that can comprise anenergy absorbing panel according to the invention is a blast boot (orfootwear generally that is designed to protect a wearer against aground-based blast—e.g., a landmine). A composite metal foam asdescribed herein can be combined with any further materials useful informing such footwear (such as aramid fiber materials, honeycombaluminum, and other blast attenuator materials). The footwear can belayered in that the composite metal foam layer can be combined withother layers, such as other blast attenuator layers, fabric layers, andthe like.

Helmets are a further example of personal protection articles accordingto the invention that can make use of energy absorbing panels includinga composite metal foam as discussed herein. The energy absorbing panelscan be particularly useful in sports headgear and military headgear toprevent penetrating head wounds and traumatic brain injury arising fromblunt force to the head. Such headgear is particularly beneficial inthat the air pockets maintained in the cells of the composite metal foamcan be effective to diffuse a significant amount of blast energy (i.e.,a blast wave or shock wave). The composite metal foam generally can beeffective to protect against impacts by ballistic projectiles (e.g.,bullets and shrapnel), impact from falls or other blunt trauma, andblast shockwaves. The composite metal foam can be layered with othermaterials, such as ceramic layers, polymer layers, cloth layers, andother metal layers, to form the protective helmet.

As seen in Example 3, an energy absorption panel according to theinvention can be particularly effecting at absorbing the energyassociated with projectiles and preventing the projectile from reachingan individual wearing the armor. Specifically, the panel (and thus anarticle incorporating the panel) can exhibit sufficient energyabsorption such that the energy of a projectile traveling at a velocityof about 200 m/s is completely absorbed by the article without fullpenetration of the projectile through the article. Depending upon thecharacteristics of projectile and angle of impact, projectiles travelingat a much greater velocity can be stopped by the panel, and articlesformed therefrom. In further embodiments, the panels and articles cancompletely absorb the energy of a projectile traveling at a velocity ofup to about 1,500 m/s while preventing full penetration of theprojectile through the article. In other embodiments, the panels andassociated articles can be effective in relation to a projectiletraveling at a velocity of up to about 1,200 m/s, up to about 1,000 m/s,or up to about 850 m/s, or in relation to a projectile traveling at avelocity of about 200 m/s to about 1,500 m/s. Such particularly canapply to a projectile having a mass of about 50 g or less, about 40 g orless, about 30 g or less, about 20 g or less, about 15 g or less, orabout 10 g or less. The mass further may be about 1 g to about 20 g,about 2 g to about 15 g, or about 5 g to about 10 g. Further, the panelsand associated articles can be effective to absorb an impact energy ofabout 2,000 Joules or greater, about 2,500 J or greater, or about 3,000J or greater.

An energy absorption panel according to the invention also can provideprotection against radiation energy. In one aspect, the energyabsorption panels can be used as components of space faring vehicles,equipment used in space, and other articles of construction used in aspace environment where exposure to radiation is greater than theaverage radiation exposure encountered on earth (e.g., space stations,lunar stations, and non-earth planetary stations). To this end, thepanels can function as lightweight structural elements useful forproviding protection from radiation, micrometeoroid impact, andtemperature extremes. Shielding is necessitated by Galactic BackgroundRadiation (GBR), consisting mostly of high-energy positively chargedparticles and solar particle effects (SPEs), the high-energy radiationthat accompanies solar flares, sunspots, and other severe variations inthe sun's surface. Structural strength is necessitated by possibleimpacts from micrometeoroids and small objects in low Earth orbit (i.e.,space debris). Excessive heat and/or cold are further concerns to spacevehicles, and relatively heavy ceramic tile structures are used as partof the current thermal protection system. The present invention providesenergy absorption panels formed of a combination of composite metalfoams (i.e., closed-cell foams) and open-cell foams, optionally with asecondary media as a filling material passing through the open cellfoam. Such multi-layer sandwich panels can be used as structural membersin the body of a spacecraft to provide protection from the triplethreats of radiation, kinetic energy, and temperature extremes.

An energy absorbing panel thus can comprise a layer of a composite metalfoam that is exterior to a layer comprising an open-cell foam. Anycomposite metal foam material as described herein can be used in anenergy absorbing panel that is effective against radiation as well askinetic energy. The composite metal foam can be positioned external tothe open-cell foam so as to provide exterior protection of the vehicleagainst impact and also to provide basic structure of the vehicle, ifdesired. An open-cell foam useful according to the invention can beformed of metals or polymers and preferably has a continuous network ofpores in communication with one another to allow for infiltration withthe secondary media.

In specific embodiments, the open-cell foam can be at least partiallyfilled with the secondary media. Any material that can be filled intothe open-cell foam and provide useful properties can be used as thesecondary media. Preferably, the secondary media inherently providesshielding to at least one type of radiation energy. For example, thesecondary media can be an aqueous media, including plain water as wellas modified water. Such modified water can include deuterated water (orheavy water), which can be useful for neutron moderation. Modified wateralso can include aqueous solutions of with a solute that can be use auseful radiation shielding material, such as boron. Waxes also can beused as the secondary media and can include plant waxes, animal waxes,and petroleum derived waxes, such as paraffins. Further, polymers(natural or synthetic) can be used, such as polyethylene.

In addition to the composite metal foam and the open-cell foam, theenergy absorption panels can include a radiation shielding material.Such material can comprise a liquid, particularly an aqueous material,such as water or a solution of boric acid. Thus, the secondary mediumcan function as the radiation shielding material. Alternately, theradiation shielding material can be included in addition to or incombination with the secondary media. The radiation shielding materialsalso can be provided as a separate layer of a solid material, such as apolymer panel coated with boron or a panel formed of boratedpolyethylene. Preferably, the radiation shielding material can comprisea material effective for shielding against one or more of neutronradiation, cosmic radiation, x-ray radiation, and gamma radiation. Boroncan be particularly useful to shield against neutron radiation.

The energy absorption panels can include a third, solid layer componentin addition to the composite metal foam layer and the open-cell foamlayer. Such further solid layer preferably is a non-foam material andcan be separate from the radiation shielding material. Useful non-foammaterials can include metals, natural polymers, synthetic polymers, andcombinations thereof. In particular embodiments, the panel can comprisethe composite metal foam layer separated from the open-cell foam layerby the non-foam layer. Further non-foam layers can be present externalto the composite metal foam layer and internal to the open-cell foamlayer. Thus, from outermost to innermost, a panel according to theinvention can comprise the following: non-foam layer/composite metalfoam layer/non-foam layer/open-cell foam layer/non-foam layer. Themultiple non-foam layers can all be formed of the same material or maybe formed of different materials. The open-cell foam layer optionallycan include secondary media.

In addition to use in space vehicles, energy absorbing panels thatshield against radiation also can be useful in relation to nuclearshielding. Spend nuclear fuel casks and reactors require structures withlight weight and good radiation capability. Transportation of spentnuclear fuels requires the use of shipping casks, which are designed toaccomplish physical containment, radiation shielding, heat removal,criticality protection, and theft protection. Approved casks must beshown to withstand impact, fire, and water immersion. An energyabsorption panel according to the present invention can be particularlyuseful in such uses because of the ability of the open-cell foam layerto provide radiation shielding and the ability of the composite metalfoam layer to provide impact protection. Again, further layers (andradiation shielding materials) can be added to the composite metal foamand the open-cell foam layers.

EXPERIMENTAL

The present invention is more fully illustrated by the followingexamples, which are set forth to illustrate the present invention andare not to be construed as limiting.

Example 1 Composite Metal Foam Prepared by Powder Metallurgy

A composite metal foam was prepared using stainless steel spheres andstainless steel powder according to the specifications provided inTables 1 and 2, respectively. The stainless steel spheres had an outsidediameter of 2.0 mm and sphere wall thickness of 0.1 mm. The spheres werecleaned in a solution of 3.0 mL HCl and 97 mL water to remove oxides,rinsed in acetone, and dried. A permanent mold made of 304 stainlesssteel and having interior dimensions of 5.1 cm.times.5.1 cm.times.10 cmwas used. The mold was prepared by coating its surfaces with a boronnitride mold release. The spheres were placed in the mold and vibratedfor 5 minutes using an APS Dynamics model 113 shaker and an APS model114 amplifier with a General Radio 1310-B frequency generator. Thepowder was added and the mold was further vibrated to completely fillthe spaces between the spheres. Total vibration time was 30 minutes at15-20 Hz.

The mold was placed in a vacuum hot press during sintering. Although nopressure was applied, the mold cap was held in place by the press, andthe thermal expansion of the spheres was used to create internalpressure to aid in the sinter of the powder. The powder and spheres weresintered using a 10° C./minute heating rate, held for 30 minutes at 850°C., further heated at a rate of 5° C./minute and held for 45 minutes at1200° C. The mold was then cooled at a rate of 20° C./minute. Thefinished composite steel foam was then removed from the mold fortesting.

Optical microscopy was performed using a Buhler Unitron 9279 opticalmicroscope equipped with a Hitachi KP-M1 CCD black and white digitalcamera. SEM images were taken with a Hitachi Ss-3200N environmental SEMequipped with EDX to determine the microstructure and chemicalcomposition of the composite metal foam. Monotonic compression testingwas performed using an MTS 810 with a 980 kN load cell and a crossheadspeed of 1.25 mm/minute.

The composite metal foam had a density of 2.9 g/cm³ (37% relativedensity) and reached a plateau stress of 113 MPa from 10-50% strain andbegan densification at around 50% strain. These and further analyticalresults are provided in Table 4 (wherein the composite metal foam fromthis example is shown as Sample 4). FIG. 15 shows a comparison of thestainless steel composite metal foam (a) before compression testing and(b) after compression testing with 60% strain.

Example 2 Composite Metal Foam Prepared by Casting

A composite metal foam was prepared by casting using low carbon steelhollow spheres and a matrix-forming liquid aluminum 356 alloy accordingto the specifications provided in Tables 1 and 2, respectively. Thesteel spheres had an outside diameter of 3.7 mm and sphere wallthickness of 0.2 mm. An open atmosphere gravity feed permanent moldcasting system made of carbon steel was used, the mold cavity havingdimensions of 121 mm×144 mm×54 mm. The mold was partially preassembledafter coating with a boron nitride powder spray to prevent oxidation tomold surfaces during preheating and for providing easy release of thesample after cooling. The spheres were placed in the mold with astainless steel mesh to hold them in place and vibrated for 10 minutesto pack the spheres into a random dense arrangement. The mold used wassimilar to that illustrated in FIGS. 7 and 8.

The aluminum alloy was melted in a high temperature furnace (3300 seriesavailable from CM Furnaces) at a temperature of 700° C. At the sametime, the mold with the hollow spheres inside was pre-heated in thefurnace to 700° C. to prevent instant solidification of the aluminumupon contact with the spheres while casting. The fully liquid aluminumalloy was then poured in the sprue tube of the heated mold. The liquidaluminum fills out the cavity while pushing the air out from the cavity.The filled mold was allowed to air cool, and the mold was disassembledand the composite metal foam removed. Testing was performed on the castcomposite metal foam as described in Example 1.

The cast composite metal foam had a density of 2.4 g/cm³ (42% relativedensity). During monotonic compression, the composite metal foam reachedan average plateau stress of 67 MPa up to 50% strain before it begandensification at around 50% strain. These and further analytical resultsare provided in Table 4 (wherein the cast, composite metal foam fromthis example is shown as Sample 2). Optical and SEM observationindicated the Al matrix had nearly filled all of the interstitial spacesbetween the steel spheres (see FIG. 12(a)). The void space due toincomplete filling of the interstitial space at the sphere pointcontacts with the Al matrix was calculated to be less than 1%.

The cast composite metal foam was tested to calculate maximum cyclicstress. Testing methods are fully described by Banhart, J. and Brinkers,W., “Fatigue Behavior of Aluminum Foams”, J. Material Science Letters,18(8), 1999, p. 617-619, and Lehmus, D., et al., “Influence of HeatTreatment on Compression Fatigue of Aluminum Foams”, Journal of MaterialScience, 37, 2002, which are incorporated herein in their entirety. Theaverage yield strength calculated, using the 0.2% offset method, was 29MPa. The maximum stress was chosen to be 85% of the reference strength.The fatigue was continued with this maximum stress for 250,000 cycleswith no apparent deformation. The maximum stress was then increased to37.5 MPa (the stress at 5% strain from the stress-strain curve). FIG. 16shows the curve for the compression fatigue test as the relation betweenstrain and the number of cycles.

The cast composite foam deformed by an initial progressive shortening,followed by collapse of the spheres starting at certain regions withpossible defects like holes or cracks, causing the subsequent failure ofthe neighboring spheres leading to the formation of macroscopic collapsebands. Visual observation of the deformed fatigue cast foam revealedthat extensive fatigue failure had occurred within the crush bands. TheS—N curve (FIG. 16) shows the initial progressive fatigue damage at theonset of an abrupt strain jump. The cast foam sample had endured1,440,000 cycles before the end of the fatigue test. Optical images ofthe cast foam taken before and during the fatigue test are shown in FIG.17.

Example 3 Effective Use of Composite Metal Foam in Body Armor

Testing was carried out to evaluate the effectiveness of an energyabsorption panel according to the invention using a composite metal foamas described herein in protecting against the ballistic energy of aprojectile. An energy absorption panel was constructed of an 8 mm thickSi₃N₄ ceramic layer backed by an 11 mm thick composite metallic foamlayer, which in turn was backed by a 6.5 mm thick polymer layer. Thecomposite metallic foam was prepared by powder metallurgy from 2.0 mmstainless steel spheres and a stainless steel matrix.

The energy absorption characteristics of the panel were tested against7.62 mm M80 ballistic ammunition. The bullet was formed of a steeljacket with a lead-antimony slug. The slug with a mass of 9.6 g wasfired from 15 feet away with 0 degree obliquity, and the projectile wascalculated to have a velocity of approximately 847 meters per second(m/s). The traveling projectile was calculated to have an associatedenergy of approximately 3500 Joules. For each of two shots, thecalculated kinetic energy at impact was based on the projectile mass andaverage velocity measurements by the following formula:

KE=(½)mV ²

wherein m is the projectile mass and V is the velocity. For shot 1, theaverage velocity was 2793 ft/s (851 m/s), and the impact energy was 3447J. For shot 2, the average velocity was 2816 ft/s (858 m/s), and theimpact energy was 3504 J. With both shots, the bullet was stopped beforecontacting the polymer back layer. Thus, the combined ceramic layer andcomposite metal foam layer were effective to dissipate the kineticenergy of the projectile and prevent the projectile from passingcompletely through the panel. Calculations estimated that of the 3475 Jof energy from the projectile (averaged between the two shots), about743 J (21.4%) of the energy was lost to deformation of the projectile,about 8.8 J (0.25%) of the energy was dissipated by the fracture of theceramic layer, about 347 J (10%) was dissipated by the motion of anyceramic and projectile fragments, and about 2376 J (68.35%) of theenergy was dissipated by deformation of the composite metal foam layer.Such calculations were based upon known methods. See, for example,Smith, P., & Hetherington, J. (1994). Blast and Ballistic Loading ofStructures. Oxford, England: Butterworth Heinemann; Ballistic Resistanceof Body Armor NIJ Standard-0101.06, National Institute of Justice, USDepartment of Justice, July, 2008. www.ojp.usdoj.gov/nij; B. K. Fink,“Performance metrics for composite integral armor,” Journal ofThermoplastic Composite Materials, vol. 13, iss. 10 (2000), pp. 417-431;David H. Lyon, Brendan J. Patton, Cynthia A. Bir, “Injury EvaluationTechniques for Non-Lethal Kinetic Energy Munitions”, Army ResearchLaboratory ARL-TR-1868, Aberdeen Proving Ground, MD (1999); I. S.Chocron Benloulo, V. Sanchez-Galvez, “A new analytical model to simulateimpact onto ceramic/composite armors,” Int. J. Impact Engineering, vol.21, no. 6, (1998), pp. 461-471; H. Nahme, V. Hohler, A. Stilp, “Dynamicmaterial properties and terminal ballistic behavior of shock loadedSi3N4 ceramics,” Journal de Physique IV, vol. 4, (1994), pp. 237-242;and A. C. Whiffin, “The Use of Flat-Ended Projectiles for DeterminingDynamic Yield Stress. II. Tests on Various Metallic Materials,”Proceedings of the Royal Society of London. Series A, Mathematical andPhysical Sciences, Volume 194, Issue 1038, pp. 300-322; the disclosuresof which are incorporated herein by reference in their entireties.

Many modifications and other embodiments of the invention will come tomind to one skilled in the art to which this invention pertains havingthe benefit of the teachings presented in the foregoing descriptions andassociated drawings. Therefore, it is to be understood that theinvention is not to be limited to the specific embodiments disclosed andthat modifications and other embodiments are intended to be includedwithin the scope of the appended claims. Although specific terms areemployed herein, they are used in a generic and descriptive sense onlyand not for purposes of limitation.

1. An energy absorption panel comprising a plurality of layers of different material, at least one layer including a composite metal foam comprising a plurality of hollow metallic spheres arranged with an interstitial space between the spheres, the interstitial space being filled with a solid metal matrix.
 2. The panel of claim 1, wherein the hollow metallic spheres are defined by one or more of the following: an average diameter of about 0.5 mm to about 20 mm; an average wall thickness that is about 1% to about 15% of the average sphere diameter; an average wall porosity of less than about 12%. 3-4. (canceled)
 5. The panel of claim 1, wherein the composite metal foam layer is defined by one or more of the following: a strength, evaluated as the plateau stress, of at least 35 MPa; a density of less than about 4 g/cm³; an energy absorption of at least about 20 MJ/m³. 6-7. (canceled)
 8. The panel of claim 1, wherein the hollow metallic spheres and the solid metal matrix are formed of the same metal or metal alloy, or wherein the hollow metallic spheres and the solid metal matrix are formed of different metals or metal alloys.
 9. (canceled)
 10. The panel of claim 1, wherein one or more of the following conditions are met: the hollow metallic spheres comprise a metal or metal alloy selected from the group consisting of iron, iron alloy, steel, aluminum, aluminum alloy, chromium, titanium, cobalt, lead, nickel, manganese, molybdenum, copper, and combinations thereof; the solid metal matrix comprises a metal or metal alloy selected from the group consisting of iron, iron alloy, steel, aluminum, aluminum alloy, chromium, titanium, cobalt, lead, nickel, manganese, molybdenum, copper, and combinations thereof; the solid metal matrix is a sintered mass of metal particles. 11-12. (canceled)
 13. The panel of claim 10, wherein solid metal matrix is a sintered mass of a mixture of metal powders formed of a first metal powder having a first average particle size and at least a second metal powder having a second, different average particle size, and wherein the particle sizes are about 1 μm to about 200 μm.
 14. (canceled)
 15. The panel of claim 1, further comprising one or both of a ceramic layer and a cloth layer.
 16. (canceled)
 17. The panel of claim 15, wherein the cloth is formed of fibers of a natural material or is formed of fibers of a synthetic material.
 18. (canceled)
 19. The panel of claim 17, wherein the synthetic material is an aramid.
 20. The panel of claim 1, further comprising a layer including an open cell foam.
 21. The panel of claim 20, further comprising a radiation shielding material.
 22. The panel of claim 21, wherein one or both of the following conditions are met: the radiation shielding material comprises a material effective against radiation selected from the group consisting of neutron radiation, cosmic radiation, x-ray radiation, gamma radiation, and combinations thereof; the open-cell foam is at least partially filled with secondary media.
 23. (canceled)
 24. The panel of claim 22, wherein one or more of the following conditions are met: the secondary media includes a radiation shielding material; the secondary media comprises a material selected from the group consisting of water, waxes, polymers, and combinations thereof; the open-cell foam is at least partially filled with the secondary media combined with a radiation shielding material; the panel further comprises one or more layers of a non-foam material; the composite metal foam layer is separated from the open cell foam layer by a non-foam layer. 25-27. (canceled)
 28. The panel of claim 24, wherein the non-foam material is selected from the group consisting of metals, natural polymers, synthetic polymers, and combinations thereof.
 29. (canceled)
 30. A personal protection article comprising the energy absorption panel of claim
 1. 31. The personal protection article of claim 30, wherein the personal protection article is defined by one or both of the following: the article is selected from the group consisting of headgear, body armor, and footwear; the energy absorption panel comprises a layer including the composite metal foam sandwiched between a ceramic layer and a cloth layer or polymer layer.
 32. (canceled)
 33. The personal protection article of claim 31, wherein the cloth is formed of fibers of a natural material, or wherein the cloth is formed of fibers of a synthetic material.
 34. (canceled)
 35. The personal protection article of claim 33, wherein the synthetic material is an aramid.
 36. The personal protection article of claim 30, wherein the article is defined by one or both of the following: exhibits sufficient energy absorption such that the energy of a projectile traveling at a velocity of about 200 m/s is completely absorbed by the article without full penetration of the projectile through the article; absorbs an impact energy of about 2,000 Joules or greater.
 37. (canceled)
 38. An armored vehicle comprising the energy absorption panel of claim
 1. 39. The armored vehicle of claim 38, wherein the energy absorption panel comprises the composite metal foam layer and a ceramic layer. 40-81. (canceled) 